PL194055B1 - Method for the manufacture of the 3-(trihalosilyl) propyl tin organic compound or a mixture of 3- (trihalosilyl) propyl tin organic compounds as well as the method for the manufacture of 3- (diorganoxyhalosilyl) propyl tin organic halides or a mixture of - Google Patents

Abstract

This invention provides: (a) new organotin functionalized silanes: (b) a solid prepared by chemically bonding organotin functionalized silanes to a solid inorganic support containing surface hydroxy groups: (c) a solid catalyst prepared from said supported organotin functionalized silane; (d) a process for conducting esterification or transesterification, and urethane, urea, silicone, and amino forming reaction utilizing said solid supported catalyst; (e) a process of separating the solid supported catalyst from the reaction products employing ligand-solid separation techniques; (f) reuse of the solid supported catalyst after being separated from the reaction products; (g) a continuous esterification or transesterification reaction or urethane, urea, silicone, or amino form.

Description

The present invention relates to a process for the preparation of organotin silanes applicable to the preparation of a solid heterogeneous catalyst for esterification or transesterification reactions and for the production of urethanes, ureas, silicones and amines.

It is known that homogeneous organotin compounds are effective catalysts for esterification, transesterification, siloxane and urethane formation reactions. However, separation of the homogeneous organotin catalysts from the reaction products is a serious problem and is often impossible or requires a special treatment that usually destroys the catalyst. Homogeneous catalysts are in the same phase, usually liquid, as the reactants and reaction products. Heterogeneous catalysts are in a phase different from the reaction products.

Many types of heterogeneous catalysts are known and have numerous advantages over homogeneous catalysts, such as the ease of separating the catalyst from the reaction products, facilitating catalyst reuse, and high mechanical and thermal stability over a wide range of operating conditions. Heterogeneous catalysts are sometimes not as selective as homogeneous catalysts. Supported metal complexes, i.e. metal complexes attached to the support by means of a chemical bond, are sometimes as selective as their homogeneous counterparts.

There are two types of supports for heterogeneous catalysts, polymeric and inorganic. Polymer supports are popular because they are easily functionalized and have a flexible structure that facilitates interactions between the active sites of the catalyst and the reactants. However, polymeric supports suffer from a number of significant drawbacks, such as poor mechanical properties, limited thermal stability, typically below 160 ° C, and lack of physical stiffness under a wide range of process conditions, which makes it difficult to control the porosity and diffusion characteristics.

Most of the known polymeric organotin compounds are not effective catalysts because they do not have the desired function for esterification or transesterification reactions and for urethane, ureas, silicones and amines formation reactions, or because tin tends to leak out of the polymer too quickly so that only a few reactions can be performed. Jiang et al. US Patent Nos. 5,436,357 and 5,561,205 disclose polymeric organotin compounds in which the organotin compound is attached to the polymer via a non-labile bond and found them to be effective in transesterification reactions. However, the use of polymeric organotin compounds is limited to reaction temperatures in the range 50 to 150 ° C and, therefore, is not expected to be effective in esterification reactions, typically carried out at temperatures above 200 ° C, when homogeneous organotin catalysts are used.

Inorganic supports have many significant advantages over polymeric supports. They have a rigid structure that allows better control of the porosity and diffusion characteristics of the carrier and are unaffected by process conditions. Thermal stability is usually limited by the stability of the complex deposited on the support, not the stability of the support as such. They also have high mechanical stability which prevents physical particle breakdown and the formation of "fines". The most commonly used inorganic supports are metal oxides because the metal oxides contain surface hydroxyl groups that can be easily functionalized. In general, two methods of attachment are used for depositing complexes on the surface of metal oxides. The first involves the use of a metal complex that contains a labile ligand capable of reacting with surface hydroxyl groups to form a reaction product in which the metal center in the complex is bonded directly to the surface through an oxygen atom according to the reaction: {E} - OH + X - M> {E} - O - M + HX, where {E} - OH is a metal oxide, M is a metal center in the complex and X is a labile ligand.

A typical preferred method for attaching a metal complex is to use a functionalized silane which contains labile ligands on the silicon atom capable of reacting with the surface hydroxyl groups of the supporting metal oxide, which can be represented by the reaction: {E} - OH + X ₃ SiY> { E} - O - SiY, where {E} - OH is a metal oxide, X is MeO, EtO, Cl, etc, and Y is a functional group.

Leaching the metal complex from the surface can be a serious problem if any degree of metal dissociation occurs under the reaction conditions.

PL 194 055 B1

Most of the known organotin compounds are not suitable for the preparation of heterogeneous catalysts because they either do not have the desired function to carry out esterification, transesterification, urethane, ureas, silicones and amines forming reactions, and cannot be modified to have such a function or not stable bonds with inorganic carriers. The synthesis of several silylmethyltin trichlorides and bis (silylmethyl) tin dichlorides are described by V. F. Mironov, E. M. Stepina, and E. M. Shiryaev, Zh. Obshch. Khim., 42, 631 (1972); V. F. Mironov, E. M. Shiryaev, V. V. Yankov, A. F. Gladchenko, and A. D. Naumov, Zh. Obshch. Khim. 44, 806 (1974); V. F. Mironov, V. I. Shiryaev, E. M. Stepina, V. V. Yankov, and V. P. Kochergin, Zh. Obshch. Khim., 45, 2448 (1975), but they do not disclose or suggest the binding of these compounds to an inorganic support or label their activity as catalysts. Similarly, N. Auner and J. Grobe in Z. Anorg. Allg. Chem., 500, 132 (1983) describe a number of 3-silylpropyltin trichlorides, but do not disclose or suggest the binding of these compounds to an inorganic support and have not determined their activity as catalysts. H. Schumann and B. Pachaly in Angew. Chem. Int. Ed. Engl., 20, 1043 (1981), H. Schumann and B. Pachaly in J. Organometal. Chem., 233, 281 (1982), H. Schumann and B. Pachaly in DE 3116643 disclose certain organotin compounds supported on an aluminum and silica support, however they do not contain the function desired for catalysis or have a labile bond between silicon and tin. S. A. Matlin and P. S. Gandham in J. Chem. Soc., Chem. Commun., 798 (1984) describe the use of organotin dimethoxide bonded to the silica surface which is effective as hydride transfer catalysts for the reduction of ketones and aldehydes.

The aim of the invention is therefore to obtain functionalized organotin silanes in which the organotin compound is linked to the silane by a stable ligand group (non-labile at both the tin end and the silicon end), at least one of the ligands at the silicon end of the molecule is labile and forms a stable silicon bond. - oxygen with the surface of inorganic carriers, and at least one of the ligands at the tin terminus of the molecule is a labile group.

The invention therefore relates to processes for the preparation of organotin silanes.

The first subject of the invention is a process for the preparation of an organotin 3- (trihalosilyl) propyltin compound or a mixture of 3- (trihalosilyl) propyltinorganic compounds, which comprises reacting 1,1-dihalosilacyclobutane with a tin halide of formula IV.

R

AND

R-Sn-R

AND

R

FORMULA 4 wherein each R is independently selected from the group consisting of F, Cl, Br, I, unsubstituted or substituted C1 to C20 alkyl, unsubstituted or substituted C1 to C20 alkenyl, unsubstituted or substituted C1 to C20 cycloalkyl C12, or unsubstituted or substituted aryl, wherein at least one R is selected from F, Cl, Br or I in the presence of a catalytically effective amount of a Lewis acid.

In one embodiment of the process, the tin halide of Formula 4 is tin tetrachloride and the reaction is carried out at an elevated temperature above 25 ° C.

In another embodiment of the process, the tin halide of formula IV is organotin trichloride in which one R is selected from alkyl, alkenyl, cycloalkyl and aryl groups.

In another embodiment of the process, the tin halide of formula IV is the cinodiorganic dichloride in which the two R substituents are selected from alkyl, alkenyl, cycloalkyl and aryl groups.

In another embodiment of the process, the tin halide of formula IV is an organocinyl chloride in which the three R substituents are selected from alkyl, alkenyl, cycloalkyl and aryl groups.

Preferably, 1,1-dichlorosilacyclobutane is used as the 1,1-dihalosilacyclobutane.

The production of the organotin silanes according to the invention is therefore a reaction

1,1-dihalosilacycloalkane (e.g. 1,1-dichlorosilacyclobutane) with organotin halide,

In the presence of a catalytically effective amount of a Lewis acid, such as aluminum trichloride, to give the corresponding 3-silapropyltin compounds.

When tin tetrachloride is used, a trihalide mixture is obtained

3- (trihalosilyl) propyltin, such as 3- (trichlorosilyl) propyltin trichloride, and di-3- (trihalosilyl) propyltin dihalide, such as 3- (trichlorosilyl) propyltin dichloride. When organotin trichloride is used, such as, for example, butyltin trichloride, the opening of the silacyclobutane ring produces organic 3- (trihalosilyl) propyltin halides, such as 3- (trichlorosilyl) propylbutyltin dichloride.

The only examples of such ring opening reactions described previously are limited to the reaction of 1,1-dichloro and 1,1-dimethylsilacyclobutane with tin tetrachloride to give the corresponding 3-silylpropyltin trichloride compounds. Although the reaction of 1,1-dichlorosilacyclobutane with tin tetrachloride has been reported by Auner and Grobe, it was found that this reaction did not result in significant conversion of the silacyclobutane to the expected organotin silane. It has surprisingly been found that a mixture of 3- (trichlorosilyl) propyltin trichloride and di-3- (trichlorosilyl) propyltin dichloride is obtained upon addition of a small amount of a suitable Lewis acid catalyst such as aluminum trichloride. When used as a Lewis acid catalyst, 1,1-dichlorosilacyclobutane reacts with organotin halides such as butyltin trichloride to open the silacyclobutane ring to give 3- (trichlorosilyl) propylbutyltin dichloride.

It has also been found that replacing the chloride function in dichlorosilacyclobutane with dialkoxy or diaryloxy functional groups eliminates the need for Lewis acid as a ring opening catalyst to form organotin silanes, and the reaction of tin tetrahalides and organotin halides with 1,1-dialkoxysilacyclobutanes occurs without the need to add a catalyst.

The second object of the invention is therefore a process for the preparation of 3- (diorganoxyhalosilyl) propyl organotin halide or a mixture of 3- (diorganoxyhalosilyl) propyl organotin halides, which comprises reacting 1,1-diorganoxysilacyclobutane of the formula 5

wherein each R is independently selected from the group consisting of unsubstituted or substituted C1 to C20 alkyl, unsubstituted or substituted C5 to C20 cycloalkyl, or unsubstituted or substituted aryl, with tin halide of formula 4

R

AND

R-Sn-R

AND

R

FORMULA 4 wherein each R is independently selected from the group consisting of F, Cl, Br, I, unsubstituted or substituted C1 to C20 alkyl, C1 to C20 alkenyl, unsubstituted or substituted, C5 to C12 cycloalkyl, unsubstituted or substituted or unsubstituted or substituted aryl, wherein at least one R is selected from F, Cl, Br or I.

In one embodiment of the process, the tin halide of Formula IV is tin tetrachloride.

In another embodiment of the process, the tin halide of formula IV is organotin trichloride, obtained by selecting one R from alkyl, alkenyl, cycloalkyl and aryl groups.

In another embodiment of the process, the tin halide of formula IV is organotin dichloride, obtained by selecting two Rs from alkyl, alkenyl, cycloalkyl and aryl groups.

PL 194 055 B1

In another embodiment of the process, the tin halide of formula IV is an organocinyl chloride obtained by selecting three Rs from alkyl, alkenyl, cycloalkyl and aryl groups.

Preferably 1,1-dimethoxysilacyclobutane is used as the 1,1-diorganoxysilacyclobutane.

This synthesis for dichlorosilacyclobutane and AlCl3 as Lewis acid catalyst can be represented by General Reaction Scheme I where n = 1 to 4. It is understood that any Lewis acid could be used.

In this general reaction scheme, a Lewis acid (aluminum trichloride) will catalyze the reaction of an organotin halide with 1,1-dihalosilacyclobutane.

The reaction will yield a product or a mixture of products depending on the value of n in the overall reaction scheme. This is represented by a series of reactions for each of the n values according to Scheme II.

Moreover, AlCl3 is known to those skilled in the art as an effective catalyst for the redistribution of organotin compounds. There are other potential molecules that can be generated by redistributing the R, Cl3Si (CH2) 3-, and Cl groups on the tin that exist in equilibrium. Accordingly, the product can be better described as a reaction product than by a structural formula. The relative amounts of the reaction products in the mixture will vary depending on the molar ratio of the reactants, that is, the molar ratio of 1,1-dichlorosilacyclobutane to be reacted with the halide.

Another synthesis not requiring the use of a Lewis acid catalyst was also discovered, involving the reaction of 1,1-dialkoxysilacyclobutane such as 1,1-dimethoxysilacyclobutane with R4-nSnCln. Reactions for different values of R4-n give mixtures of the reaction products shown in Scheme II, except that the chlorides on the silicon atom are replaced by RO- groups and there is no need to use a Lewis acid catalyst.

PL 194 055 B1

The reactivity of the tin halide decreases with increasing the number of organic functional groups on the tin, i.e., the reactivity decreases in the order of SnCl4> RSnCl3> R2SnCl2 and R3SnCl, especially in non-catalyzed reactions.

The production of organotin silanes according to the invention and their chemical bonding to a solid support containing a metal oxide with surface hydroxyl groups is disclosed below and in the examples of at least one preferred embodiment.

A solid, supported organotin compound obtained by reacting the organotin silanes of the invention with solid metal oxides containing surface hydroxyl groups, such as glass, silica, mica, silica gel, aluminum oxide, aluminosiloxanes, kaolin, zirconium oxide and chromium oxide, has proved to be an excellent heterogeneous catalyst for esterification or transesterification reactions or for the formation of urethanes, ureas, silicones and amines.

The supported functionalized organotin silanes have been found to be a class of excellent heterogeneous catalysts for esterification or transesterification or urethane, ureas, silicones and amines forming reactions.

The method of carrying out the esterification or transesterification reaction and the formation of urethanes, ureas, silicones and amines comprises the steps of the reaction of the non-solid phase reactants of the esterification or transesterification reaction or the formation of urethanes, ureas, silicones and amines in the presence of a catalytically effective amount of solids. , supported on the organotin silane obtained by the process of the invention, and the separation of the solid catalyst from the non-solid phase containing the reaction products.

The method of conducting a continuous esterification or transesterification reaction and the formation of urethanes, ureas, silicones and amines involves the continuous reaction of the reactants of the esterification or transesterification reaction and the formation of urethanes, ureas, silicones and amines in a reactor containing a catalytically effective amount of a solid, supported on a support organotin silane obtained by the process of the invention as a catalyst and the continuous separation of the non-solid phase containing the reaction products from the solid catalyst.

A heterogeneous catalyst containing an organotin silane or a functionalized organotin silane is prepared by chemically bonding (supporting) an organotin or functionalized organotin silane to a solid metal oxide containing surface hydroxyl groups via at least one metal-O-Si bond. Functionalized heterogeneous organotin silanes can be synthesized either by binding the organotin silane to a solid support or by binding the functionalized organotin silane to a solid support and then improving the catalytic functionality by replacing at least one of the labile groups on the tin in the organotin silane with groups of substituents.

The catalytic functionality of the organotin or functionalized silanes can be enhanced by converting them to functionalized organotin silanes and supported functionalized organotin silanes, respectively. This is done by replacing the labile tin-related group by reaction with a reagent selected from the group consisting of hydroxides, oxides, carbonates, bicarbonates, phosphates, phosphinates, sulfates, salts of organic acids, sulfonates, alkali metals and alkaline earth metals, alcohols, phenols and salts of inorganic and organic acids. The result is a class of supported functionalized organotin silanes which are excellent heterogeneous catalysts for esterification or transesterification or urethane, ureas, silicones and amines formation reactions. A key condition for the catalytic properties of this functional group is the formation of a labile bond with tin under conventional esterification or transesterification reaction conditions or urethane, ureas, silicones and amines forming reaction. Catalytically active groups on the tin atom include F, Cl, Br, I, MO-, OR, benzyl, vinyl, allyl, hydride, hydroxyl, sulfide, sulfate, carbonate, phosphate, phosphite, phosphonate, sulfonate, mercaptan, mercaptanic acid residue , mercapto alcohol or mercaptoester, substituted or unsubstituted C1 to C20 carboxylates. However, preferred groups are Cl, OR, oxide, hydroxide, sulfonate, or substituted or unsubstituted C1 to C20 carboxylates.

Supported organotin silanes and functionalized supported organotin silanes have proved to be excellent heterogeneous catalysts for esterification or transesterification or urethane, urea, silicones and amine formation reactions.

PL 194 055 B1

An improved esterification or transesterification or urethane, ureas, silicones or amine forming reaction process consists in reacting in the non-solid phase of the reactants of the esterification or transesterification reaction or the urethane, ureas, silicones or amines forming reaction, and is characterized by reacting non-phase reactants solid in the presence of a catalytically effective amount of a solid, supported organosilane catalyst containing the organotin silane or a functionalized organotin silane, and the non-solid phase containing the reaction products is separated from the solid catalyst. As a result, a tin-catalyzed reaction product is obtained which nevertheless contains very little tin after a phase separation operation in which the solid catalyst is separated from the non-solid reaction product. Phase separation operations such as liquid-solid and gas-solid phase separations are well known unit operations in chemical engineering and are used in practice. Several known unit operations using phase differences to separate substances are filtration, centrifugation, settling and trapping. Further, separation may be performed while the solid catalyst is in a reactor, such as a packed bed or column to which the non-solid reactants are added and from which the non-solid reaction products are removed, thereby separating the non-solid reaction products from the solid catalyst. . The reactor containing the solid catalyst can be used to continuously carry out the esterification or transesterification reaction or the formation of urethanes, ureas, silicones or amines. This is accomplished by continuously adding the non-solid reactants to the reactor containing the catalyst and continuously removing the stream containing the non-solid reaction products.

In both continuous and batch operation after separation from the solid catalyst, the reaction products have surprisingly low levels of tin impurities, typically below 100 ppm, and may be below 10 ppm. This purity is achieved by simple phase separation in which the solid (heterogeneous) catalyst is separated from the non-solid, usually liquid, reaction products. This purity is also related to the fact that the tin catalyst is not easily extractable from the solid support due to the strong bond between the support and the organotin silane achieved by the M-O-Si bond. Reducing or eliminating tin impurities is important when the product of the esterification or transesterification reaction or urethane, ureas, silicones or amines forming reaction is to be used in contact with food, for example in containers or for human consumption, for example in the form of pharmaceutical products.

The heterogeneous organosilane catalyst is a solid, supported organotin silane or a functionalized organotin silane, obtained as the reaction product of the organotin or functionalized organotin silane with a solid support having a metal oxide containing hydroxyl groups on the surface of the solid support. Examples of suitable metal oxide materials are glasses such as silica, mica, silica gel, alumina, aluminosiloxanes, kaolin, titanium oxide, zirconia, and chromium oxide. Suitable carriers may be solid, hollow or porous particles of such materials or composites having such substances on the particle surface. The present invention is independent of the shape and size of the solid support. Although the typical shape of the supports are beads, any convenient shape and size may be selected and used in practicing the invention, taking into account factors such as an appropriate surface area to weight ratio and / or the ease of separation of the solid catalyst from the non-solid reaction products.

One or more of the labile groups (i.e., F, Cl, Br, I or OR) on the tin of the supported catalyst containing organotin silane is preferably replaced with a group having improved catalytic properties. This can be done by reacting the organotin silane, before or after bonding to the support (preferably after bonding), with a wide variety of reagents such as hydroxides, oxides, carbonates, bicarbonates, phosphates, phosphates, sulfates, organic acid salts, alkali metal and metal sulfonates. alkaline earths, and by reaction with alcohols, phenols and inorganic and organic acids and other reagents known to those skilled in the art for the purpose of substituting the halide function in the organotin halide. This results in the replacement of a labile group (i.e. F, Cl, Br, I or OR) on the tin with a functional group such as an oxide, hydroxide, carboxylate, hydrogen carboxylate, sulfate, organic salt, sulfonate, phenate, inorganic or organic acids, mercaptides , phosphate, phosphite, phosphate and carbonate. Although the organotin silane with the labile tin halide group is catalytically active, preferably the halide group in the organotin silane is replaced with another functional group by the above-mentioned reaction. It is advantageous to introduce an improved catalytic function into the organotin silane after it has been reacted with a support containing metal oxide, as this avoids displacement

A functional group also includes a labile group or groups in the silane. The labile group or groups on the silane is better used to form a Me-O-Si bond for chemically attaching the organotin silane to the support.

Synthesis of functionalized organotin silanes of type A.

Comparative example by A.

Reaction of 1,1-dichlorosilacyclobutane with tin tetrachloride

1,1-Dichlorosilacyclobutane (7.14 grams) and tin tetrachloride (13.70 grams) were transferred to a test tube under nitrogen. The tube was sealed, placed in an oil bath and held for 18.5 hours at 132 ° C. Analysis of the reaction mixture by ¹¹⁹ Sn and ²⁹ Si NMR showed that the reaction was not going to take place.

P r z k ł a d 1.

AlCl3 catalyzed reaction of 1,1-dichlorosilacyclobutane with tin tetrachloride.

1,1-Dichlorosilacyclobutane (6.77 grams, 0.048 moles), tin tetrachloride (13.58 grams, 0.051 moles), and aluminum trichloride (0.44 grams, 0.0033 moles) were transferred to a tube under nitrogen. The tube was sealed, placed in an oil bath and kept at 133 ° C for 24 hours. Analysis of the reaction mixture by ²⁹ Si NMR showed 100% conversion of the 1,1-dichlorosilacyclobutane. ¹¹⁹ SnNMR: 21.1 mole% Cl3Si (CH2) 3SnCl3, 25.8 mole% [Cl3Si (CH2) 3] 2SnCl2 and 53.1 mole% tin tetrachloride.

P r z k ł a d 2.

AlCl3 catalyzed reaction of 1,1-dichlorosilacyclobutane with tin tetrachloride.

1,1-Dichlorosilacyclobutane (28.54 grams, 0.202 moles), tin tetrachloride (26.62 grams, 0.102 moles), and aluminum trichloride (1.00 grams, 0.0075 moles) were transferred to a 100 mL flask under nitrogen. The mixture was heated to reflux for 18 hours. Analysis of the reaction mixture by ¹¹⁹ Sn NMR showed that all of the tin tetrachloride had reacted to 95.1 mole% [Cl3Si (CH2) 3] 2SnCl2 and 4.1 mole% Cl3Si (CH2) 3SnCl3.

P r z k ł a d 3.

AlCl3 catalyzed reaction of 1,1-dichlorosilacyclobutane with butyltin trichloride.

1,1-Dichlorosilacyclobutane (12.79 grams, 0.907 moles), butyltin trichloride (25.59 grams, 0.907 moles), and aluminum trichloride (0.70 grams, 0.0052 moles) were transferred under nitrogen to a 100 mL flask. The mixture was heated to reflux for 25 hours. Analysis of the reaction mixture by GC-MS showed 46.8 area% Cl3Si (CH2) 3SnCl2 and 34.4 area% [Cl3Si (CH2) 3] 2Sn (Bu) Cl.

P r z k ł a d 4.

Reaction of 1,1-dimethoxysilacyclobutane with tin tetrachloride.

1,1-Dimethoxysilacyclobutane (30.0 grams, 0.227 moles), tin tetrachloride (76.0 grams, 0.294 moles), and toluene (170 mL) were transferred to a flask under nitrogen and stirred for 18 hours at 25 ° C. The mixture was then heated to reflux for 6 hours. The reaction product, represented by the formula (MeO) 2ClSi (CH2) 3SnCl3, was isolated by removal of the solvent and vacuum distillation at 123-126 ° C at 1 Torr (? 1.333x10 ⁵ Pa). Elemental analysis results: 30.9% Sn and 7.76% Si.

P r z l a d 5.

Reaction of 1,1-dimethoxysilacyclobutane with butyltin trichloride.

1,1-Dimethoxysilacyclobutane (30.0 grams, 0.227 moles) and butyltin trichloride (64.1 grams, 0.227 moles) were transferred to a flask under nitrogen and stirred for 30 hours at 80 ° C. The reaction product, represented by the formula (MeO) 2ClSi (CH2) 3Sn (Bu) Cl2, was isolated by removal of the solvent and vacuum distillation at 160 ° C at 1 Torr (? 1.333x10 ⁵ Pa). Elemental analysis results: 24.0% Sn and 6.55% Si.

Synthesis of B-type functionalized organotin silanes. P r y k ł a d 6.

Reaction of (MeO) 3SiCH2Cl with SnCl2.

20.0 grams of (MeO) 3SiCH2Cl, 11.11 grams of SnCl2, and 1.30 grams of n-Pr4NCl were transferred to a flask under nitrogen and heated at 154 ° C for 3 hours. The reaction mixture was filtered and then distilled under vacuum at 88-90 ° C at 2 Torr (2.666x10 ⁵ Pa). Elemental analysis of the isolated product showed 32.4% Sn, 7.61% Si and 29.2% Cl corresponding to the formula (MeO) 3SiCH2SnCl3.

PL 194 055 B1

Binding of the organotin compound with silica

Drying Silica (Preparation of the carrier)

98.0 grams of Davisil 646 silica gel (supplier WR Grace) was placed in a liter flask and heated to 95 ° C at 1.8 Torr (? 2.506x10 ⁵ Pa) for 5 hours to give the silica gel which was used in the examples.

Comparative example B.

Attempt to deposit monobutyltin trichloride on silica.

grams of dried silica was transferred under dry nitrogen to a 250 mL flask. 75 mL of toluene was added to the reaction flask via a syringe followed by 10.4 mL (6.14 grams) of monobutyltin trichloride. The mixture was refluxed under nitrogen for 18 hours. The volatiles were then removed in vacuo to give a precipitate. 8.52 grams of the solid was Soxhlet extracted with methanol for 18.5 hours. The wet precipitate was then dried in vacuo. Elemental analysis for tin content gave 0.13% Sn. The calculated percentage of tin assuming complete conversion of monobutyltin trichloride to the product represented by the formula {Si} -O-Sn (Bu) Cl2 is 8.5% Sn.

Comparative example C.

Attempted deposition of tin tetrachloride on silica.

11.0 grams of dried silica and 7.16 grams of tin tetrachloride were transferred under nitrogen to the reaction flask and 30 ml of toluene was added. The mixture was heated to reflux for 5 hours, cooled to room temperature and filtered. The precipitate was Soxhlet extracted with methanol for 20 hours and dried in vacuo to give 8.82 g of a solid. Elemental analysis of the reaction product gave 0.74% Sn.

P r z k ł a d 7.

Binding of [Cl3Si (CH2) 3] 2SnCl2 mixture on silica

6.00 grams of dried silica, about 30 ml of toluene, and 4.99 grams of [Cl3Si (CH2) 3] 2SnCl2 from Example 3 were transferred to a flask under nitrogen and heated to reflux for 5 hours. The reaction mixture was cooled and filtered, and the solids Soxhlet extracted with methanol for 24 hours. The precipitate was then dried in vacuo. Elemental analysis gave 5.5% Sn.

P r z k ł a d 8.

Binding of (MeO) 2ClSi (CH2) 3SnCl3 on silica

101.6 grams of dried silica, 259.5 grams of toluene, and 16.62 grams of (MeO) 2ClSi (CH2) 3SnCl3 from Example 4 were transferred to a flask under nitrogen and heated to reflux for 5 hours. The reaction mixture was cooled, filtered and the solids Soxhlet extracted with methanol for 30 hours. The precipitate was then dried in vacuo. Elemental analysis was 3.98% Sn and 2.12% Cl.

P r z h o m 9.

Binding of (MeO) 2ClSi (CH2) 3Sn (Bu) Cl2

61.8 grams of dried silica, 158.8 grams of toluene, and 17.9 grams of (MeO) 2ClSi (CH2) 3Sn (Bu) Cl2 from Example 5 were transferred to a flask under nitrogen and heated to reflux for 5 hours. The reaction mixture was cooled, filtered and the solids Soxhlet extracted with methanol for 24 hours. The precipitate was then dried in vacuo. Elemental analysis gave 6.02% Sn and 3.23% Cl.

P r z k ł a d 10.

Binding of (MeO) 3ClSiCH2SnCl3 on silica

4.04 grams of (MeO) 3SiCH2SnCl3 from Example 6, 26.92 grams of dried silica and 68.66 grams of toluene were transferred to a flask under nitrogen and heated to reflux for 5 hours. The reaction mixture was cooled and filtered, and the solids Soxhlet extracted with methanol for 24 hours. The precipitate was then dried in vacuo. Elemental analysis was 3.83% Sn and 1.91% Cl.

P r x l a d 11.

Reaction of (MeO) 2ClSi (CH2) 3SnCl3 bound on silica with sodium acetate.

5.56 grams of (MeO) 2ClSi (CH2) 3SnCl3 bound on silica from Example 8, 3.60 grams of sodium acetate trihydrate and 60 ml of methanol were transferred to a flask and heated to reflux for 2 hours. The precipitate was filtered off then Soxhlet extracted with methanol for 20 hours.

The precipitate was then dried in vacuo. Elemental analysis gave 4.11% Sn and 0.04% Cl.

PL 194 055 B1

Esterification reactions

General procedure: 111.09 grams of phthalic anhydride (0.75 mol), 234.41 grams of 2-ethylhexanol (1.80 mol) and an amount of catalyst corresponding to 116.1 mg of tin in the catalyst per 100 grams of phthalic anhydride were transferred to a flask at 1 liter capacity, equipped with a Dean and Stark separator. The reaction flask was purged with nitrogen for 15 minutes and the temperature of the reaction mixture was raised to 220 ° C. The reaction mixture began to boil at 175 ° C and reaction times were counted from the time the mixture reached 175 ° C. The amount of unreacted acid at the end of the reaction was expressed as the acid number (mg KOH per gram of sample).

P r z k ł a d 12.

Esterification reactions using heterogeneous organotin catalysts

Catalyst Acid number Response time (h) Example 7 0.19 7 Example 8 0.13 6 Example 9 0.14 6 Example 10 0.09 4 Example 11 0.11 5

P r z l a d 13.

Esterification reactions with catalyst recycling

Esterification reactions were performed as described in the general procedure. At the end of each reaction, the liquid reaction product was separated from the solid heterogeneous organotin catalyst by a simple liquid-solid separation operation by filtration. This was done by removing the product from the reaction flask through a filter tube inserted into the reaction flask, leaving the catalyst in the flask along with a small amount of reaction product. Then phthalic anhydride and 2-ethylhexanol were added and a second esterification reaction was carried out with the same catalyst that remained in the flask. Reuse of the catalyst with additional reagents was repeated up to six times, monitoring the acid value and time to determine how long it took to convert completely. The results are shown in the table below.

Catalyst Example 7 Example 9 Original 0.8 (6) 0.09 (4) 1 0.08 (5.5) 0.05 (4.5) 2 0.04 (5.5) 0.11 (5) 3 0.15 (5.5) 0.17 (6) 4 3.3 (6) 0.24 (6) 5 0.11 (6) 2.8 (6) 6 0.14 (6)

(The reaction time is given in brackets after the acid value)

Claims (12)

A method for producing an organo-3- (trihalosilyl) propyltin compound or a mixture of organo-3- (trihalosilyl) propyltin compounds, characterized by reacting 1,1-dihalosilacyclobutane with a tin halide of formula 4 PL 194 055 B1 R AND R-Sn-R AND R FORMULA 4 wherein each R is independently selected from the group consisting of F, Cl, Br, I, unsubstituted or substituted C1 to C20 alkyl, unsubstituted or substituted C1 to C20 alkenyl, unsubstituted or substituted C5 to C5 cycloalkyl C12, or unsubstituted or substituted aryl wherein at least one R is selected from F, Cl, Br or I in the presence of a catalytically effective amount of a Lewis acid. 2. The method according to p. The process of claim 1, wherein the tin halide of formula 4 is tin tetrachloride and the reaction is carried out at an elevated temperature above 25 ° C. 3. The method according to p. The process of claim 1, wherein the tin halide of formula 4 is organotin trichloride in which one R is selected from alkyl, alkenyl, cycloalkyl and aryl groups. 4. The method according to p. The process of claim 1 wherein the tin halide of formula IV is cinodiorganic dichloride in which the two R substituents are selected from alkyl, alkenyl, cycloalkyl and aryl groups. 5. The method according to p. 3. The process of claim 1, wherein the tin halide of formula IV is organotinchloride in which the three R substituents are selected from alkyl, alkenyl, cycloalkyl and aryl groups. 6. The method according to p. A process as claimed in any one of the preceding claims, characterized in that 1,1-dichlorosilacyclobutane is used as the 1,1-dihalosilacyclobutane. Process for the preparation of 3- (diorganoxyhalosilyl) propyl organotin halide or a mixture of 3- (diorganoxyhalosilyl) propyl organotin halides, characterized by reacting 1,1-diorganoxysilacyclobutane of formula 5 wherein each of R is independently selected from the group consisting of consisting of unsubstituted or substituted C1 to C20 alkyl unsubstituted or substituted cycloalkyl C5 to C12 or unsubstituted or substituted aryl, with a tin halide of formula 4 R AND R-Sn-R AND R FORMULA 4 wherein each R is independently selected from the group consisting of F, Cl, Br, I, unsubstituted or substituted C1 to C20 alkyl, unsubstituted or substituted C1 to C20 alkenyl, unsubstituted or substituted C5 to C5 cycloalkyl C12, unsubstituted or substituted aryl, wherein at least one R is selected from F, Cl, Br or I. 8. The method according to p. The process of claim 7, wherein the tin halide of formula IV is tin tetrachloride. 9. The method according to p. The process of claim 7, wherein the tin halide of formula IV is organotin trichloride obtained by selecting one R from the alkyl, alkenyl, cycloalkyl and aryl groups. PL 194 055 B1 10. The method according to p. The process of claim 7, wherein the tin halide of formula IV is cinodiorganic dichloride, obtained by selecting two Rs from alkyl, alkenyl, cycloalkyl and aryl groups. 11. The method according to p. The process as claimed in claim 7, wherein the tin halide of formula IV is organotinchloride, obtained by selecting three Rs from alkyl, alkenyl, cycloalkyl and aryl groups. 12. The method according to p. A process according to any of the preceding claims, characterized in that 1,1-dimethoxysilacyclobutane is used as the 1,1-diorganoxysilacyclobutane.